4.6 Article

Excited-State Dynamics of Bis(tetraethylammonium) Di-μ-bromo-dibromodicuprate(I) Thin Films

Journal

MOLECULES
Volume 28, Issue 23, Pages -

Publisher

MDPI
DOI: 10.3390/molecules28237841

Keywords

molecular salts; halocuprates; ultrafast laser spectroscopy; triplet emission

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In this study, thin films of a novel organic-inorganic halocuprate were prepared and their relaxation processes in the excited state were investigated. The compound exhibited blue emission with a long excited-state lifetime. Additionally, the time scales for absorption and emission, as well as the relaxation processes of carriers and phonons, were studied.
Organic-inorganic halocuprates based on monovalent copper are promising luminescent compounds for optoelectronic applications; however, their relaxation processes in the excited electronic state are severely underexplored. In this contribution, we prepare thin films of bis(tetraethylammonium) di-mu-bromo-dibromodicuprate(I) [N(C2H5)4]2[Cu2Br4], abbreviated (TEA)2Cu2Br4, which features a molecular salt structure containing discrete [Cu2Br4]2- anions. This compound, which has an absorption peak at 283 nm, displays a blue, strongly Stokes-shifted emission with a peak at 467 nm. Transient photoluminescence (PL) experiments using broadband emission detection and time-correlated single-photon counting (TCSPC) both find an excited-state lifetime of 57 mu s at 296 K. UV-Vis transient absorption experiments at 296 K covering time scales from femto- to microseconds provide evidence for the formation of the T1 state through intersystem crossing from S1 with a time constant of 184 ps. The triplet state subsequently decays to S0 predominantly by phosphorescence. In addition, the time constants for carrier-optical phonon scattering (1.8 ps) and acoustic phonon relaxation (8.3 ns and 465 ns) of (TEA)2Cu2Br4 are provided.

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